2-(2,2-diethoxyethyl)isoindole-1,3-dione

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of phthalimidoacetaldehyde diethyl acetal (790 mg, 3.0 mmol) in acetic acid (2.5 mL) was added conc.HCl (0.1 mL). The mixture was stirred for 80 minutes at 50° C. The reaction mixture was cooled to room temperature, to which was added (3aR*,10aS*)-9-benzyl-2,3,3a,4,9,10a-hexahydrobenzo[b]cyclopenta [e][1,4]diazepin-10(1H)-one (877 mg, 3.0 mmol), and the mixture was stirred for 25 minutes at room temperatures. To this solution was added, sodium triacetoxyborohydride (805 mg, 3.9 mmol) portionwise, and the mixture was stirred for 40 minutes at 45° C. The reaction mixture was cooled to room temperatures, to which were added dichloromethane (10 mL) and water (10 mL). The aqueous layer was separated, and the organic layer was washed with water and a saturated aqueous solution of sodium hydrogencarbonate, dried over magnesium sulfate and subjected to filtration. The filtrate was concentrated under reduced pressure. The concentrate was purified by silica-gel column chromatography (chloroform-methanol 20:1), followed by crystallization from ethanol-hexane to give 0.80 g (yield 57%) the titled compound. The sample for analytical experiment was prepared by recrystallization from dichloromethane-ethanol-hexane. m.p. 142.0°-142.6° C. The reaction mixture was cooled to room temperature, to which the mixture was stirred for 25 minutes at room temperatures To this solution was added The reaction mixture was cooled to room temperatures, to which The aqueous layer was separated the organic layer was washed with water a saturated aqueous solution of sodium hydrogencarbonate, dried over magnesium sulfate subjected to filtration The filtrate was concentrated under reduced pressure The concentrate was purified by silica-gel column chromatography (chloroform-methanol 20:1) followed by crystallization from ethanol-hexane

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Phthalimidoacetaldehyde diethyl acetal (100 g, 0.38 mol) and 1 N hydrochloric acid (600 ml) was mixture was stirred at reflux temperature for 5 min. or until a homogeneous solution is obtained. The reaction mixture was cooled and the precipitate was filtered off and dried in vacuo at 50° C. for 16 h which afforded 63.3 g (88%) of phthalimido-acetaldehyde as a solid. at reflux temperature for 5 min. until a homogeneous solution is obtained The reaction mixture was cooled the precipitate was filtered off dried in vacuo at 50° C. for 16 h which

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 50.0 g (190 mmol) of 2-(phthalimido)acetaldehyde diethyl acetal in 300 mL of toluene was treated with 150 mL of 50% aqueous trifluoroacetic acid and the mixture was stirred vigorously at ambient temperature for 72 h. The solution was concentrated in vacuo and 100 mL of ethyl acetate was added. The white precipitate was filtered off and washed with ice-cold ethyl acetate (100 mL) to give 30.0 g (78%) of the title compound. The solution was concentrated in vacuo and 100 mL of ethyl acetate was added The white precipitate was filtered off washed with ice-cold ethyl acetate (100 mL)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 50.0 g (190 mmol) of 2-(phthalimido)acetaldehyde diethyl acetal in 300 mL of toluene was treated with 150 mL of 50% aqueous trifluoroacetic acid and the mixture was stirred vigorously at ambient temperature for 72 h. The solution was concentrated in vacuo and 100 mL of ethyl acetate was added. The white precipitate was filtered off and washed with ice-cold ethyl acetate (100 mL) to give 30.0 g (78%) of the title compound. The solution was concentrated in vacuo and 100 mL of ethyl acetate was added The white precipitate was filtered off washed with ice-cold ethyl acetate (100 mL)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Water (50 mL) and trifluoroacetic acid (50 mL) were added to a solution of phthalimidoacetaldehyde diethyl acetal (30.0 g, 114 mmol) in chloroform (200 mL), and the reaction mixture was stirred at room temperature for 48 hours. The aqueous layer was separated, adjusted to pH 7 with the addition of sodium carbonate, and extracted with several portions of dichloromethane. The combined organic fractions were dried over magnesium sulfate, filtered, and concentrated under reduced pressure to provide 14.2 g of (1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)acetaldehyde as a white solid. The aqueous layer was separated adjusted to pH 7 with the addition of sodium carbonate extracted with several portions of dichloromethane The combined organic fractions were dried over magnesium sulfate filtered concentrated under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-(2,2-diethoxyethyl)isoindoline-1,3-dione (40.00 g, 0.15 mol) was dissolved in 85% formic acid (150 mL) and the mixture was stirred for 2 h at rt. After tlc analysis indicated full conversion to the aldehyde (2,4-DNP stain used for visualization), the solvent was removed and the resultant solid was dried at 150 mm torr vacuum to give 2-(1,3-dioxoisoindolin-2-yl)acetaldehyde (27 g, 95%). the solvent was removed the resultant solid was dried at 150 mm

反応条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A three-necked round-bottomed flask fitted with an efficient stirrer and a reflux condenser was charged with potassium phthalimide (150 g, 0.81 mol) and 2-bromo-1,1-diethoxy-ethane (196 g, 1.0 mol) and DMF (500 mL). The stirrer was started and the mixture was heated for about 3-4 h in an oil bath maintained at 150° C. The solvent DMF was removed under reduced pressure. The residue was purified by column chromatography to afford pure 2-(2,2-diethoxyethyl)isoindoline-1,3-dione (185 g, yield 87%). 1H NMR (400 MHz, MeOD): 1.16 (t, 6H), 3.48-3.60 (m, 2H), 3.68-3.75 (m, 2H), 3.76-3.89 (d, 2H), 4.89 (t, 1H), 7.68-7.75 (m, 2H), 7.85-7.96 (m, 2H). MS (E/Z): 264 (M+H+). A three-necked round-bottomed flask fitted with an efficient stirrer and a reflux condenser the mixture was heated for about 3-4 h in an oil bath The solvent DMF was removed under reduced pressure The residue was purified by column chromatography